Rustproofing composition



Dec. 26, 1939. J. c. ZIMMER ET AL 2,184,952

RUSTPROOFING COMPOSITION v Filed April so, 195e Ox/DA Tf ON 7 0 WagN-DEy-SEE/ 26 25 l Z6 I 6 l y N* 50A@ EVA PQQQATQR LIN AMD WATER 3T c 5 man E Vass L. l WATER OUTLET WATER /NLET 55 n- ,51 1 43 44 y E 1 'v sns-An WEC/(5R T'OEJEc-ro-g SSEL 4| 57 f fm; 41 L55 T@ 1 d r wach/Ew.

S7-ORAGE STEAM INLET l TA NK Y STfAM vzzff/EA TER. l v cleans Bof-Tons .S ejnDc-E :DRAW GTF Patented Dec. 26, 1939 UNITED STATES PATENT OFFICE 2,184,952 USTPROOFIN G COMPOSITION of Delaware Application lApril 30, 1938, Serial No. 205,192

8Claims.

10 tillation of acids obtained by the catalytic, liquid phase, low temperature oxidation of wax at atmospheric pressure. In' order to obtain a better understanding of the, method employed in obtaining this residue, a drawing has been included..

15 showing diagrammatically the various essential steps involved.

Referring to the accompanying drawing, numeral I designates a batch oxidation tower, preferably constructed oi aluminum and operated at atmospheric pressure and at about 100-130 C.

Wax containing an oxidation catalyst (such as manganese salt or oxide) is introduced into the tower through line 2. Air is then blown through che heated wax utuabout io-soa, of the waxv u is converted into saponiiiable product, the spent air issuing from line4 being cooled and the water separated from other liquid products in separator 6. 'Ihe latter are then withdrawn together with the oxidation product from tower I through lines 5 and 1 and run into agitator 8 wherein caustic or other suitable saponifying agent is introduced through line 8'. 'I'he resultingmixture is drawn through line I0 into saponiner I I which is generally maintained at about 100 lbs. pressure by the introduction of high pressure steam.

After the saponication is completed, the mixture is ted into extractor I3 through line I2, some low molecular weight alcohol (such as isopropyl or methyl alcohol) being added through line i4 n in order to prevent any emulsication in the extractor. The purpose of the extraction step is to remove the saponied material from the unsaponifled portion'. -This is accomplished by extracting at about 50-60 C. the saponiiled mixu ture (containing the alcohol demulsifler) with a hydrocarbon such as gasoline or naphtha which is pumped from gasoline storage I8 by pump I9 through line I1 into extractor I3 countercurrent to the saponied mixture. The gasoline solution 50 of unsaponied material is then drawn off the top of the tower I3, while the aqueous saponifled solution is removed at the bottom of extractor I3 by line 2| and fed into the soap evaporator 28. The purpose of this vessel is to distill oil the a1- cohol and some water through line 20 into the storage vessel I5 for reuse in the extraction operation.

The alcohol-free soap solution is subsequently drawn off evaporator 28 through line 30 into agitator 3l wherein sulfuric acid or other suitable 5 acid is added through pipe 32 for regenerating the acid oxidation products. After the mineral acid has been reacted, the mixture is drawn out through pipe 33 into separator 34. Here a separation occurs. The bottom layer consisting 1'0 chiey of water containing soluble salts is drawn olf the bottom at 35, while the top layer consisting essentially of the acid products is removed through line 38, washed ywith water in scrubber 31 andfed into crude acid storage 4I) by means of 1| line 39.

Now returning to the extractor I3, the gasoline solution of unsaponiiiable matter is fed into gasoline still 22 through line 20 and the gasoline taken overhead through line 23 and stored in gas- 20 oline storage I8 for re-use. The bottoms from stili 22 are drawn out through pipe 24 and fed. into the wax stripper still 25, steam being fed in through line 38. The unsaponiable matter, be-I ing free of light ends, is returned by line 21 into 25 the wax feed line 2 leading to the oxidation tower for recycling, while the lower boiling products (consisting essentially of water and gasoline) carried overhead by line 26, are returned to the gasoline still 22 by line 20. 30

Again returning to the crude acid-in storage tank 40, the product is led into steam preheater 4I, thence into flash tank 43 via pipe 42. The low boiling acids are distilled over at about 165 C. into receiving tank 45, both vessels 43 and 45 35 being kept at a vacuum of about 10 mm. of mercury. These low boiling acids, ranging from about Cs to Cm may be drawn of! at 46 as the rst cut. The bottoms from flash tank 43 are drawn through line 41 into the Wecker still 48 which 40" is maintained at about 240-260 C. bottoms temperature at l0 mm. vacuum. Steam is fed into this still through lines 49, and the still is heated by gas ring at 50. The overhead from this still is condensed in vessel 52 equipped with an ejec- 45 tor for maintaining vacuum, and the second acid fraction is drawn off at 54. The bottoms from the Wecker still are drawn oil at 55 and stored in tank 56. These bottoms may be drawn of! at 51 for use in connection with the present inven- 5,) tion, as will be further outlined.

The Wecker still bottoms so obtained exhibit many interesting and useful properties heretofore lacking in prior art products. In the rst place.

the iodine numbers and molecular weights of 55' wwmmm/ these bottoms show that they decidedly unsaturated. Their iodine values range around 18-20 ogs/gm. or more. They show acid numbers of about 50-55 and saponication numbers of 150-160. 'I'heir composition approximates 40% r freeacids, 55% esters and lactones, and 5% un- Molecular weight.......-....-......

saponiable. The acids separated from these bottoms by cold caustic extraction analyze approximately as follows:

ms.KOH/c.. 180-190 Saponiflcation value (pressure) mg. Molecular weight (avera3e) 60o-650 The unsaponiied portion analyses approximately as follows:

iso-e Saponication value (pressure) ms. KOH/s... 110-120 Iodine value ---csa/g..- Acetyl value mas. KOH/g..- Naphtha soluble --.per cent.. 97.5

a5. might also be emphasized that substantially no aldehydes are present in the' product. One test showed the presence of only 0.003% total aldehydes (calculated as formaldehyde). Aldehydes and aldehyde-acids are characteristic of vapor 'phase oxidized products which have been found to be much less suitable for the purpose of this invention.

One specic embodiment of the invention involves the addition of 5 to 60% or more of these ,bottoms to petrolatum, heavy lubricating oils, "or volatile naphthas. Another embodiment involves the addition to the above mixture of 5 to 20% of cil soluble (mahogany) petroleum sulfonate soaps such as the sodium soaps of sulfuric acids obtained in the treating of lubricating oils with fuming sulfuric acid for the production of white oils. The mahogany soaps so added are capable of absorbing moisture as well as producing an emulsifiablecomposition. An excellent product, however, is prepared by the usev of the bottoms, mahogany sulionates, and degras. The following examples serve to illustrate many of the superior features of these compositions:

Emmple 1 A number of polished steel plates were coated with compositions prepared according to this invention and exposed in the open for four months in a roof weathering test.` The following data were obtained:

Condition of plate Composition after e months exposure Poor--very rusty.

KOH/3... B20-230 Example 2 Composition Dtbizore C. 10 degres (neutral) 10 o maneggio p (50% oil)..-

y soa napht a (Varsol) D. l degres 10 o mahogany soap (50% oil) 10% Wecker still bottoms.--

F. 10 a demas (neu a naphtha (Varsol) It will be observed from the above data that, for outside exposure, composition "E" containing Wecker still bottoms and degres in naphtha was most suitable.

Example 3 The following treated cleaned steel plates were subjected to humidier and water spray tests. The humidier test consisted in suspending slushed steel plates (2 x 4" x 11W) in an atmosphere of humidity at 100 F. in a special cabinet (4' x 2' x 2') and noting the time in hours for rusting of the plates to occur. The atmospheric conditions were maintained with air bubbled at the rate of cu. ft./hr. through water at F. and directed against a baille plate to obtain uniform distribution in the cabinet and to knock out the entrained water droplem. This test is indicative of service for indoor use.

The water spray test was carried out according to the U. S. Navy spray test for evaluation of rust preventives with the following modifications: The slushlng compound was applied by dipping sand blasted steel plates at a temperature consistent with ease of application, and the oven heating was omitted. The intermittent water shower was continued until rusting occurred. This test is indicative of service for outdoor use:

Telt

Composition Humidi- Water iier spray css 22 degres eu Wecker sun bommai no4 100+ K n phthwi'i)"" f egras neu f 7.5% Wecker still bottoms 8 4o 86 naphths (Vanni) L. 30 degres (neutral) 72 2 7() lubricating oil... M. 16 degres (neutral)--.

16 Wecker still bottoms. 312 2% 70 lubricating oil A carefm. study of the above data win reveal that the use of Wecker still bottoms greatly improves resistance to rusting both indoors and outdoors. For external use, a 5% concentration of these bottoms (Sample I) appears to be too low, although it still showed good service for outdoor use. Wecker still bottoms compositions containing mahogany suli'onates (Sample G) showed exceptional resistance to indoor weathering. Samples L and M illustrate the superiority of Wecker still bottoms when compared to degras which is used commercially for this purpose. The

water spray test results should not be taken too seriously, since these two samples contain nonvolatile lubricating oil which is washed off readily by the water. Such compositions would ordinarily be employed for inside use.

Example 4 Another series of samples was tested as in Example 2:

707 cold test petrolatum O. 30%onon-saponiiiable roduct'obtained by liquid phase pressure oxi ation oi wax 75 70% cold test petrolatum P. 30% Wecker still bottoms- 600 70% cold test petrolatum The above results show that the sample (P) containing the unsaturated Wecker still bottoms obtained by atmospheric pressure oxidation of wax were able to withstand rusting 72 hours longer than the sample containing the same amount of acids obtained by pressure oxidation of wax (N), and 525 hours longer than the sample (O) containing the unsaponiable product. It was also found thatv the pressure oxidized product had a poor solubility in petrolatum, while the Wecker still bottoms showed good solubility at ordinary temperatures.

These Wecker still bottoms may be used as such, or separated into saponiable or unsaponifiable portions, which may likewise be employed separately or in combination with each other. The bottoms may also be neutralized with lime. soda, alumina, and other metal bases prior to compounding. Although as little as and as high as '10% or more may be employed, it is found preferable to use -30% o1' these compounds. 0

The other compounding agents which may be employed with these materials are naphth'as, light oils such as keroseneor gas oil, lubricating oils, their solvent extracts or ralnates, petrolatum, paraiiin waxes, bright stocks, cracked residues, such as cracking coil tar, asphalte, etc., as well as voltolized hydrocarbons and fats, fatty oils, resins, dyes, metal soaps, e. g., aluminum stearate, naphthenate, calcium rosinate, zinc degras soap, tin oleate, cobalt linoleate, chromium oleate, manganese naphthenate, and the like.

Antioxidants such as naphthols, naphthylamines. phenol suldes and disuldes, sulfur, sulfurized fats, cresols, aliphatic amines and hydroxy amines and naphthenic amines may be added.

Wecker still bottoms, as disclosed herein, are preferably prepared by the oxidation oi' purified paramn waxes, although petrolatum may be employed as a raw materiaLespecially if it is deoiled to contain not over about 5% oil. Foots oil obtained by sweating of crude parafiin wax is also a satisfactory raw material. 'I'his oil more closely resembles paramn wax in structure than the usual lubricating oils.

The compositions disclosed herein are also suitable for use in cutting oils, plan.; sprays, drawing compositions, roll oils, emulsiilable oils, greases, etc.

'Ihe above description and examples are intended to be illustrative only, and any modifications of or Variations therefrom which conforms to the spirit of the invention is intended to be included within the scope of the claims:

We claim:

l. A rustprooiing composition comprising a hydrocarbon coating vehicle containing at least 5% of an aldehyde-free unsaturated distillation residue of acids produced by the low temperature liquid phase catalytic oxidation of hydrocarbon wax at atmospheric pressure.

2. A rustproong composition comprising a hydrocarbon vehicle containing 5 to 60% of an unsaturated vacuum distillation residue produced by the low temperature liquid phase catalytic oxidation of hydrocarbon wax at atmospheric pressure and having the following approximate analysis:

Iodine number cgs./g 18-20 Acid number mg. KOH/g.- 50-55 Saponification -value mg. KOH/g..- 150-160 3. A rustproong composition comprising a hydrocarbon vehicle containing 5-60% of an unsaturated vacuum distillation residue produced by the low temperature liquid phase catalytic oxidation of hydrocarbon wax at atmospheric.

pressure, said residue containing approximately 40% free acids, 55% esters and lactones, and 5% unsaponifiable matter, and yielding, upon saponiiication with cold caustic potash, products having the following approximate composition:

Liberated acids from Unsaponiiled saponitled matter Average molecular weight Iodine number Neutralization value.. 85. 5 Baponiiication value under pressure. Acetyl value v Percent 0 25 Percent H l2. 05

' distillation residue of acids produced by the lowtemperature liquid phase catalytc oxidation of hydrocarbon wax at atmospheric pressure, about 5 to 30% of degras, and about 5 to 30% of mahogany soap.

7. A composition according to claim 6 in which the petroleum normally liquid hydrocarbon is a light hydrocarbon.

8. A composition according to claim 6 inwhich the petroleum hydrocarbon is a heavy hydrocarbon.

JOHN C. ZllVilVmR.. JACK B. CRUTCHEIELD. 

